Bis‐hydrophilic and functional triblock terpolymers based on polyethers: Synthesis and self‐assembly in solution

A well‐defined triblock terpolymer, poly(ethylene glycol)‐block‐poly(allyl glycidyl ether)‐block‐poly(tert‐butyl glycidyl ether) (PEG‐b‐PAGE‐b‐Pt‐BGE), with a narrow molar mass distribution has been synthesized by sequential living anionic ring‐opening polymerization. Afterward, the PAGE block was modified via thiol‐ene chemistry and different sugar moieties or cysteine as a model compound for peptides could be covalently attached to the polymer backbone. The solution self‐assembly of the obtained bis‐hydrophilic triblock terpolymers in aqueous media has been studied in detail by turbidimetry, dynamic light scattering, and transmission electron microscopy (TEM and cryo‐TEM). © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

PEG‐b‐PtBA‐b‐PHEMA well‐defined amphiphilic triblock copolymer: Synthesis,self‐assembly,and application in drug delivery

A series of well‐defined amphiphilic triblock copolymers, poly(ethylene glycol)‐b‐poly(tert‐butyl acrylate)‐b‐poly(2‐hydroxyethyl methacrylate) (PEG‐b‐PtBA‐b‐PHEMA), were synthesized via successive atom transfer radical polymerization (ATRP). ATRP of tBA was first initiated by PEG‐Br macroinitiator using CuBr/N,N,N′,N″,N′″‐pentamethyldiethylenetriamine as catalytic system to give PEG‐b‐PtBA diblock copolymer. This copolymer was then used as macroinitiator to initiate ATRP of HEMA, which afforded the target triblock copolymer, PEG‐b‐PtBA‐b‐PHEMA. The critical micelle concentrations of obtained amphiphilic triblock copolymers were determined by fluorescence spectroscopy using N‐phenyl‐1‐naphthylamine as probe. The morphology and size of formed aggregates were investigated by transmission electron microscopy and dynamic light scattering, respectively. Finally, an acid‐sensitive PEG‐b‐PtBA‐b‐P(HEMA‐CAD) prodrug via cis‐aconityl linkage between doxorubicin and hydroxyls of triblock copolymers with a high drug loading content up to 38%, was prepared to preliminarily explore the application of triblock copolymer in drug delivery. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis,physicochemical characterization,and self‐assembly of linear,dibranched, and miktoarm semifluorinated triphilic polymers

Linear, dibranched, and miktoarm amphiphiles containing both hydrophobic and fluorophilic moieties were synthesized and characterized in an attempt to elucidate the relationship between semifluorinated amphiphile structure and aggregate behavior in aqueous solution. For the linear and dibranched amphiphiles, there was an exponential decrease in critical aggregation concentration (CMC) and a logarithmic increase in core microviscosity with increasing length of the fluorocarbon segments; while the miktoarm architecture produced no notable trend in microviscosity or CMC. Furthermore, the linear and dibranched surfactants showed enhanced kinetic stability, dissociating more slowly in the presence of human serum than did either the dibranched or miktoarm amphiphiles. Finally, encapsulation studies with the hydrophobic drug paclitaxel (PTX) showed that the ability to solubilize and retain PTX increased with the presence and with the increasing size of the fluorocarbon moiety for both the linear and dibranched amphiphiles, while no such trend was observed for the miktoarm amphiphiles. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3324–3336     

Self‐assembly of well‐defined amphiphilic polymeric miktoarm stars,dendrons, and dendrimers in water: The effect of architecture

Five polymeric architectures with a systematic increase in architectural complexity were synthesized by “click” reactions from a toolbox of functional linear polymers and small molecule linkers. The amphiphilic architectures ranged from a simple 3‐miktoarm star block copolymer to the more complex third generation dendrimer‐like block copolymer, consisting of polystyrene (PSTY) and polyacrylic acid (PAA). Micellization of these architectures in water at a pH of 7 under identical ionic strength gave spherical micelles ranging in size from 9 to 30 nm. Subsequent calculations of the PSTY core density, average surface area per PAA arm on the corona‐core interface, and the relative stretching of the PAA arms provided insights into the effect of architecture on the self‐assembly processes. A particular trend was observed that with increased architectural complexity the hydrodynamic diameter, radius of the core in the dry state and the aggregation number also increased with the exception of the third generation dendrimer. On the basis of these observations, we postulate that thermodynamic factors controlling self‐assembly were the entropic penalty of forming PSTY loops in the core counterbalanced by the reduction in repulsive forces through chain stretching. This results in a greater number of aggregating unimers and consequently larger micelle sizes. The junction points within the architecture also play an important role in controlling the self‐assembly process. The G3 dendrimer showed results contradictory to the aforementioned trend. We believe that the self‐assembly process of this architecture was dominated by the increased attractive forces due to stretching of the PSTY core chains to form a more compact core. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6292–6303, 2009     

Single chain self‐assembly of well‐defined heterotelechelic polymers generated by ATRP and click chemistry revisited

Well‐defined heterotelechelic poly(styrene) carrying thymine/diaminopyridine (DAP) (M_n,SEC = 9300, PDI = 1.04) and Hamilton wedge (HW)/cyanuric acid (CA) (M_n,SEC = 8200, PDI = 1.04) bonding motifs are prepared via a combination of controlled/living radical polymerization and copper catalyzed azide/alkyne “click” chemistry and are subsequently self‐assembled as single chains to emulate—on a simple level—the self‐folding behavior of natural biomacromolecules. Hydrogen nuclear magnetic resonance (¹H NMR) in deuterated dichloromethane and dynamic light scattering analyses provides evidence for the hydrogen bonding interactions between the α‐thymine and ω‐DAP as well as α‐CA and ω‐HW chain ends of the heterotelechelic polymers leading to circular entropy driven single chain self‐assembly. This study demonstrates that the choice of NMR solvent is important for obtaining well‐resolved NMR spectra of the self‐assembled structures. In addition, steric effects on the HW can affect the efficiency of the self‐assembly process. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and self‐assembly of thermotropic block copolymer with long alkyl tethered cage silsesquioxane in the side chain

Thermotropic POSS‐containing poly(methacrylate) with long alkyl chain tethered polyhedral oligomeric silsesquioxane (POSS) in the side chain and the block copolymers (PMMA‐b‐PMAC11POSS) were developed by through living anionic polymerization. The resulting polymers indicated a phase transition temperature at 112 °C from spherocrystal to isotropic phase. The POSS‐containing polymer segments tended to form matrix of microphase‐separated nanostructures in the bulk even in the very low volume fraction, for instance, PMMA cylindrical nanostructure was obtained by PMMA₁₇₅‐b‐PMAC11POSS₁₁ (?_PMAC11POSS = 0.44). The control of thin film morphology was carried out by not only solvent annealing, but also thermal annealing, resulting in the formation of well‐ordered dot‐ and fingerprint‐type nanostructures. This is the first report in a series of POSS‐containing block polymers that are capable for thermal annealing to generate well‐ordered microphase‐separated nanostructures in thin films. The novel thermotropic POSS‐containing block copolymer offers a promising material for block copolymer lithography. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Preparation of polyhedral oligomeric silsesquioxane‐containing block copolymer with well‐controlled stereoregularity

Preparation of functional domains with a spacing of 10 nm is a benchmark set to fabricate next‐generation electronic devices. Organic–inorganic block copolymers form well‐ordered microphase separations with very small domain sizes. The design and preparation of a novel block copolymer consisting of syndiotactic polymethyl methacrylate (st‐PMMA) and polyhedral oligomeric silsesquioxane (POSS)‐functionalized polymethacrylate, designated as st‐PMMA‐b‐PMAPOSS, which can recognize functional molecules, are reported. The st‐PMMA segments form a helical structure and encapsulate C₆₀ in the helical nanocavity, leading to the formation of an inclusion complex. Although the ordering of the domains is not high, C₆₀ domains that are in a quasi‐equilibrium state, with about 10‐nm domain spacings, are generated using st‐PMMA‐b‐PMAPOSS that can recognize functional molecules. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2181–2189     

Synthesis,characterization, and self‐assembly of comb‐dendronized amphiphilic block copolymers

Novel amphiphilic comb‐dendronized diblock copolymers composed of hydrophobic Percec‐type dendronized polystyrene block and hydrophilic comb‐like poly(ethylene oxide) grafted polymethacrylate P(PEOMA) block were designed and synthesized via two steps of atom transfer radical polymerization (ATRP). The comb‐like P(PEOMA) prepared by ATRP of macromonomers (PEOMA) with two different molecular weights (M_n = 300 and 475) were used to initiate the sequent ATRP of dendritic styrene macromonomer (DS). The molecular weights and compositions of the obtained block copolymers were determined by ¹H NMR analysis. The copolymers with relatively narrow polydispersities (1.27–1.38) were thus obtained. The bulk properties of comb‐dendronized block copolymers were studied by using differential scanning calorimetry, polarized optical microscopy and wide‐angle X‐ray diffraction (WAXD). Similar to dendronized homopolymers, the block copolymers exhibited hexagonal columnar liquid‐crystalline phase structure. By using such amphiphilic comb‐dendronized block copolymers as building blocks, the rich self‐assembly morphologies, such as twisted string, vesicle, and large compound micelle (LCM), were obtained in a mixture of CH₃OH and THF. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4205–4217, 2008     

Effects of graft length and density of well‐defined graft polymers on the thermoresponsive behavior and self‐assembly morphology

A series of well‐defined thermoresponsive graft polymers with different lengths and graft densities, poly(glycidyl methacrylate)‐graft‐poly(N‐isopropylacrylate) (PGMA‐g‐PNIPAM), were successfully prepared by combination of controlled/living free radical polymerization and click chemistry. Effects of grafting length and density on the thermoresponsive behavior, aggregating mean diameter, and self‐assembly morphology are systematically investigated. The thermosensitive characteristics of graft polymers in aqueous solution prove that the length and graft density had positive co‐relationship with the lower critical solution temperature value and mean diameter of micelles as well as the size distribution, while the effect of graft length of polymers is more significant than that of density. Transmission electron microscopy analysis shows that the conformations of PGMA₄₅‐g‐PNIPAM₂₀ and PGMA₄₅‐g‐PNIPAM₄₆ with longer length and bigger grafting density in aqueous solutions are spherical nanoparticles with the increasing trend of the diameters, while that of PGMA₄₅‐g‐PNIPAM_{(73, 50%)} shows a spherical‐like morphology, which indicates that the graft length and density have a significant effect on the mean diameter of micelle but not on the self‐assembly morphology. These results reveal that to obtain desired thermoresponsive behavior and self‐assembly morphology of functional polymers, it is essential to design and fabricate the structure of graft polymers with proper length and graft density. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2442–2453     

Synthesis of well‐defined side chain fullerene polymers and study of their self‐aggregation behaviors

Monoalkynyl‐functionalized fullerene was precisely synthesized starting with pristine fullerene (C₆₀) and characterized by multiple techniques. Methyl methacrylate and 6‐azido hexyl methacrylate were then randomly copolymerized via reversible addition fragmentation chain transfer polymerization to build polymer backbones with well‐controlled molecular weights and copolymer compositions. Finally, these two moieties were covalently assembled into a series of well‐defined side chain fullerene polymers (SFPs) via the copper‐mediated click reaction which was verified by Fourier transform infrared spectroscopy and ¹H NMR. The fullerene loadings of the resultant polymers were estimated by thermogravimetric analysis and UV–vis spectroscopy, demonstrating consistent and high conversions in most of the samples. The morphology studies of the SFPs were performed both in solution and on solid substrates. Very intriguing self‐aggregation behaviors were detected by both gel permeation chromatography and dynamic light scattering analyses. Furthermore, the scanning electron microscopic images of these polymers showed the formation of various supramolecular nanoparticle assemblies and crystalline‐like clusters depending on the fullerene contents and polymer chain lengths. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3572–3582     

Synthesis and self‐assembly of multiple‐responsive magnetic nanogels

In this paper, temperature and pH‐sensitive interpenetrating polymer network (IPN) nanogels (NGs) were firstly prepared, and magnetic hybrid NGs were made through in‐situ precipitation of Fe²⁺ and Fe³⁺ into the IPN NGs. Under the optimized condition, the resulting hybrid NG dispersion with up to 17.3 wt% magnetite was stable, while the size distribution of the NGs is broad due to the formation of Fe₃O₄ nanoparticles outside the NGs. In order to synthesize relatively uniform magnetic NGs, magnetite content was reduced to 8.1 wt% magnetite. The NGs with 8.1 wt% magnetite can quickly self‐assemble into colloidal crystals induced by magnet, while such NGs slowly self‐assembled into colloidal crystals without external magnetic field. Furthermore, the reflection wavelength of the self‐assembled magnetic NGs showed red‐shift with increasing pH and temperature.     

Synthesis of amphiphilic homopolymers and their self‐assembly into acid‐responsive polymeric micelles

This contribution presents a strategy for preparing amphiphilic homopolymers as building blocks for self‐assembly into supramolecular nanostructures. The synthesis begins with norbornene monomers containing oligoethylene glycols on the side chains. Ring‐opening metathesis polymerization of the monomers and subsequent dihydroxylation afford water‐soluble dihydroxylated poly(norbornene)s (PNBs). Amphiphilic modifications of the hydrophilic PNBs can be achieved by reacting 1,2‐diols on the backbones with hydrophobic dodecanals to form acetal linkages. The self‐assembly of the resulting amphiphilic PNB homopolymers affords polymeric micelles whose morphologies can be tuned by breaking the acetal linkages under acidic conditions. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3804–3808     

Supramacromolecular self‐assembly: Chain extension,star and block polymers via pseudorotaxane formation from well‐defined end‐functionalized polymers

Dibenzo‐24‐crown‐8‐terminated polystyrene ( 5 ) was chain extended to “dimeric” 8 by pseudorotaxane formation with a ditopic guest, α,ω‐bis[p‐(N‐benzylammoniomethyl)phenoxy]heptane bis(hexafluorophosphate) ( 7 ). The three‐armed star polymer 11 was similarly formed by complexation of the dibenzo‐24‐crown‐8‐terminated polystyrene ( 5 ) with a tritopic secondary ammonium salt, 1,3,5‐tris[p‐(benzylammoniomethyl)phenyl]benzene tris(hexafluorophosphate) ( 10 ). Another three‐armed star polymer 13 was self‐assembled from dibenzo‐24‐crown‐8‐terminated polystyrene ( 5 ) and a tetratopic paraquat compound, 1,2,4,5‐tetrakis{p‐N‐[(N′‐methyl‐4,4′‐bipyridinium)methylphenyl]}benzene octakis(hexafluorophosphate) ( 12 ). The above chain extension and star polymer formation processes seemed to be cooperative; that is, the second and third complexation steps proceed with stepwise higher efficiencies than statistically expected. Dibenzo‐24‐crown‐8‐terminated polystyrene ( 5 ) was chain extended with secondary ammonium terminated polystyrene 14 , forming 16 , and also self‐assembled with a secondary ammonium ion terminated polyisoprene 15 to form supramolecular block copolymer 17 . These processes were examined by NMR, mass spectrometry and viscometery. Thus, although binding in these systems is not particularly strong (association constants <10⁴ M^?1), these examples provide proof‐of‐principle that pseudorotaxane formation is a viable concept for chain extension and self‐assembly of novel types of block copolymers and star polymers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3518–3543, 2009     

Well‐defined amphiphilic polymethylene‐b‐poly(acrylic acid) diblock copolymers: New synthetic strategy and their self‐assembly

Well‐defined amphiphilic polymethylene‐b‐poly (acrylicacid) diblock copolymers have been synthesized via a new strategy combining polyhomologation and atom transfer radical polymerization (ATRP). Hydroxyl‐terminated polymethylenes (PM‐OH) with different molecular weights and narrow molecular weight distribution are obtained through the polyhomologation of dimethylsulfoxonium methylides following quantitative oxidation via trimethylamine‐N‐oxide dihydrate. Subsequently, polymethylene‐based macroinitiators (PM‐MIs M_n = 1,300 g mol^?1 [M_w/M_n = 1.11] and M_n = 3,300 g mol^?1 [M_w/M_n = 1.04]) are synthesized by transformation of terminal hydroxyl group of PM‐OH to α‐haloester in ～100% conversion. ATRPs of tert‐butyl acrylate (t‐BuA) are then carried out using PM‐MIs as initiator to construct PM‐b‐P(t‐BuA) diblock copolymers with controllable molecular weight (M_n = 8,800–15,800 g mol^?1 M_w/M_n = 1.04–1.09) and different weight ratio of PM/P(t‐BuA) segment (1:1.7–1:11.2). The amphiphilic PM‐b‐PAA diblock copolymers are finally prepared by hydrolysis of PM‐b‐P(t‐BuA) copolymers and their self‐assembly behavior in water is preliminarily investigated via the determination of critical micelle concentrations, dynamic light scattering, and transmission electron microscope (TEM). © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Advances in square arrays through self‐assembly and directed self‐assembly of block copolymers

This review covers recent advances in developing square arrays in thin films using block copolymers. Theoretical and experimental results from self‐assembly of block copolymers in bulk and thin films, directed self‐assembly of block copolymers confined in small wells, on substrates with arrays of posts, and on chemically nanopatterned substrates, as well as applications as nanolithography are reviewed. Some future work and hypothesis are discussed. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Novel amphiphilic homopolymers containing meta‐ and para‐pyridine moieties with living characteristics and their self‐assembly

Amphiphilic monomers containing the isomeric pyridine moieties 3‐(4‐vinylphenyl)pyridine (3VPPy) and 4‐(4‐vinylphenyl)pyridine (4VPPy) were synthesized using the Suzuki coupling reaction. A living anionic polymerization of 3VPPy and 4VPPy was successfully performed under various conditions to overcome the limitations of anionic polymerization and to compare their properties with those of poly(2‐(4‐vinylphenyl)pyridine) as reported previously. Several characteristics of the resulting isomeric P3VPPy and P4VPPy were studied, such as thermal stability, solubility, and the living nature. The block copolymerization of 4VPPy with 2‐vinylpyridine and MMA was carried out without additive to estimate the nucleophilicity of P4VPPy and to confirm its living nature. Additionally, each amphiphilic homopolymer of P3VPPy and P4VPPy containing both a hydrophilic pyridine unit and a hydrophobic styrene unit was tested for self‐assembly behavior in a mixed solvent (THF/water) and monitored with TEM and SEM. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3458–3469     

Synthesis and self‐assembly of amphiphilic macrocyclic block copolymer topologies

We demonstrated the synthesis of miktoarm star block copolymers of AB, AB₂, and A₂B, in which block A consisted of linear poly(tert‐butyl acrylate) (P^tBA) and block B consisted of cyclic polystyrene. These structures were produced using the atom transfer radical polymerization to make telechelic polymers that, after modification, were further coupled together by copper‐catalyzed “click” reactions with high coupling efficiency. Deprotection of P^tBA to poly(acrylic acid) (PAA) afforded amphiphilic miktoarm structures that when micellized in water gave vesicle morphologies when the block length of PAA was 21 units. Increasing the PAA block length to 46 units produced spherical core‐shell micelles. AB₂ miktoarm stars packed more densely into the core compared to its linear counterpart (i.e., a four times greater aggregation number with approximately the same hydrodynamic diameter), resulting in the PAA arms being more compressed in the corona and extending into the water phase beyond its normal Gaussian chain conformation. These results show that the cyclic structure attached to an amphiphilic block has a significant influence on increasing the aggregation number through a greater packing density. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

Synthesis,characterization, and self‐assembly of ion‐bonded A2B rod‐coil copolymer with oligo(para‐phenyleneethynylene) as rod segment

Supramolecular A₂B rod‐coil copolymer, composed of two polystyrene (PSt) arms and one oligo(para‐phenyleneethynylene) (OPE) arm linked via ionic bond, has been designed and successfully synthesized. First, a trifunctional initiator, methyl 1,3‐bis(bromomethyl)benzonate, was prepared and used to initiate the polymerization of styrene under atom transfer radical polymerization (ATRP) condition to provide polystyrene (PSt) carrying monoester group at the middle of polymer chain. Then, the ester group was transferred into tertiary amino group to give amino‐functionalized PSt, (PSt)₂? N(CH₃)₂. Subsequently, the ion‐bonded rod‐coil copolymer, (PSt)₂? OPE, was obtained by the reaction of (PSt)₂? N(CH₃)₂ with carboxy‐terminated OPE (OPE? COOH). The resulting copolymer was characterized by nuclear magnetic resonance (NMR), Fourier transformer infrared (FTIR), and gel permeation chromatography (GPC) techniques. Vesicles and spherical micelles were generated from this supramolecular rod‐coil copolymer through the manipulation of the initial polymer concentration in toluene. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7667–7676, 2008     

Synthesis,characterization, and aqueous self‐assembly of amphiphilic poly(ethylene oxide)‐functionalized hyperbranched fluoropolymers

Complex amphiphilic polymers were synthesized via core‐first polymerization followed by alkylation‐based grafting of poly(ethylene oxide) (PEO). Inimer 1‐(4′‐(bromomethyl)benzyloxy)‐2,3,5,6‐tetrafluoro‐4‐vinylbenzene was synthesized and subjected to atom transfer radical self‐condensing vinyl polymerization to afford hyperbranched fluoropolymer (HBFP) as the hydrophobic core component with a number‐averaged molecular weight of 29 kDa and polydispersity index of 2.1. The alkyl halide chain ends on the HBFP were allowed to undergo reaction with monomethoxy‐terminated poly(ethylene oxide) amine (PEO_x‐NH₂) at different grafting numbers and PEO chain lengths to afford PEO‐functionalized HBFPs [(PEO_x)_y‐HBFPs], with x = 15 while y = 16, 22, or 29, x = 44 while y = 16, and x = 112 while y = 16. The amphiphilic, grafted block copolymers were found to aggregate in aqueous solution to give micelles with number‐averaged diameters (D_av) of 12–28 nm, as measured by transmission electron microscopy (TEM). An increase of the PEO:HBFP ratio, by increase in either the grafting densities (y values) or the chain lengths (x values), led to decreased TEM‐measured diameters. These complex, amphiphilic (PEO_x)_y‐HBFPs, with tunable sizes, might find potential applications as nanoscopic biomedical devices, such as drug delivery vehicles and ¹⁹F magnetic resonance imaging agents. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3487–3496, 2010     

Synthesis,self‐assembly,fluorescence, and thermosensitive properties of star‐shaped amphiphilic copolymers with porphyrin core

Star‐shaped amphiphilic poly(ε‐caprolactone)‐block‐poly(oligo(ethylene glycol) methyl ether methacrylate) with porphyrin core (SPPCL‐b‐POEGMA) was synthesized by combination of ring‐opening polymerization (ROP) and atom transfer radical polymerization (ATRP). Star‐shaped PCL with porphyrin core (SPPCL) was prepared by bulk polymerization of ε‐caprolactone (CL) with tetrahydroxyethyl‐terminated porphyrin initiator and tin 2‐ethylexanote (Sn(Oct)₂) catalyst. SPPCL was converted into SPPCLBr macroinitiator with 2‐bromoisobutyryl bromide. Star‐shaped SPPCL‐b‐POEGMA was obtained via ATRP of oligo(ethylene glycol) methyl ether methacrylate (OEGMA). SPPCL‐b‐POEGMA can easily self‐assemble into micelles in aqueous solution via dialysis method. The formation of micellar aggregates were confirmed by critical micelle formation concentration, dynamic light scattering, and transmission electron microscopy. The micelles also exhibit property of temperature‐induced drug release and the lower critical solution temperature (LCST) was 60.6 °C. Furthermore, SPPCL‐b‐POEGMA micelles can reversibly swell and shrink in response to external temperature. In addition, SPPCL‐b‐POEGMA can present obvious fluorescence. Finally, the controlled drug release of copolymer micelles can be achieved by the change of temperatures. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011